Third Weekly Examination

Chemistry S-20ab

July 14, 2014

Name:
circle
Section TF: one: Christina Esty Kaleb Peter Rahul

Important Notes:

1. This exam consists of 8 problems on 8 pages, plus this cover sheet, and one page for scratch work at
the end of the exam.

2. All answers must be written in the spaces provided. Do not write anything in red ink. Answers
written on the back of a page will not be graded. Anything written on the scratch page will not be graded.

3. You are allowed to use a set of molecular models for this exam.

Problem Score

1. ____________ / 12

2. ____________ / 12
Total Score:
3. ____________ / 12

4. ____________ / 12
________________ / 100
5. ____________ / 14

6. ____________ / 14

7. ____________ / 12

8. ____________ / 12
 1 Name:
1. Each of the following transformations can be carried out in no more than three steps. Fill in the reagents
required for each step. If a step is not needed, please put an "X" through that step.

1.
OH O
a)
Ph Ph
2.

3.

1.
H3C HO OH
CH3
b)
2. H3C
H3C CH3 H
H3C

3. (+/-)

1.
H3C OH
c) H3C S
2. S CH3

3.

1.

d)
2.

3.

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 2 Name:
2. Fill in each box with the starting material or single major organic product of the indicated
transformation. For full credit, you must use each reagent in a reasonable way. Be sure to indicate
stereochemistry if it is relevant!

1. H2 / Lindlar O
a)
2. Hg(OAc)2
3. NaBH4

O
1.
O
2. H+ workup
b) Ph
3. CrO3, dry H

1. OsO4, H2O
2. HIO4
c)
3. NaBH4, EtOH

1. Na0, NH3 (liq.)

3. NaOMe, MeOH

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 3 Name:
3. You have just synthesized a new compound, and the following spectroscopic data are obtained:
• From the mass spectrum, you deduce that the molecular formula is: C5H10O2
• The infrared spectrum is:

4000 3000 2000 1500 1000 500

O H C N O H C N
or or or C O C C or
C O C C
N H C C N H C C

• The proton NMR spectrum is:

6H
3H

1H

6 5 4 3 2 1 0
PPM
Draw your best choice for the structure of this molecule in the box below.

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 4 Name:
4. You have just synthesized a new compound, and the following spectroscopic data are obtained:
• From the mass spectrum, you deduce that the molecular formula is: C9H10N2
• The infrared spectrum is:

From the infrared spectrum, circle the types of bonds From the infrared spectrum, circle the types of
that are definitely present: bonds that are definitely absent:

O H C N O H C N
or or or C O C C or
C O C C
N H C C N H C C

• The proton NMR spectrum is:

6H

2H 2H

Draw your best choice for the structure of this molecule in the box below.

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 5 Name:

5. a) Both of the molecules shown below undergo rapid, intramolecular reactions to yield the same cationic
product. Predict the product of these one-step reactions and show the curved arrows required for each.

Et
CH3 HN
H
N Cl
Et Cl CH3

cation A
b) Cation A undergoes a reaction with aqueous sodium hydroxide to give the enantiomerically pure product
shown below. Provide an arrow-pushing mechanism. Hint: the pKa of NH4+ is about 9.
Et
HN as a pure
NaOH
enantiomer
H2O HO
CH3

cation A

c) Under acidic conditions, Cation A reacts with water to give a different product than was formed in part (b).
Predict the product and provide a mechanism for its formation. You may ignore stereochemistry here.

H+, H2O

cation A

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 6 Name:

6. When the internal alkyne shown below is treated with a very strong base, a carbanion intermediate can be
formed. Treatment of this intermediate with D2O gives a mixture of two products, A and B:

H3C H3C D
1. NaNH2 2. D2O D H3C
CH3 C + CH3
H3C CH3
H3C H3C
(+/-) A (+/-) B (+/-)
a) Provide a complete curved-arrow mechanism for both steps of this reaction sequence in the space below.
Your mechanism should account for the formation of both products A and B.

b) Product B (shown below) is treated with one equivalent of Br2. Predict the product of this reaction and
provide a curved-arrow mechanism for the transformation.

D
H3C Br Br
B CH3
(+/-) H3C

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 7 Name:

7. Provide a complete synthesis of the following desired product from the indicated starting material. You may
also use any inorganic or organic reagents you wish, but all carbons from the starting material must end up
in the product. You do not need to show any mechanisms. The best answer will require six or fewer total
steps.

Starting Material:

S S

Desired Product

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 8 Name:

8. Provide a complete synthesis of the following desired product from the indicated starting materials. You
may use any inorganic or organic reagents you wish, but all carbons from the starting materials must end up
in the product. You do not need to show any mechanisms. You may ignore stereochemistry. The best
answer will require seven or fewer total steps.

Starting Materials:

and

Desired Product
(you may ignore stereochemistry)

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SCRATCH PAPER ONLY - NOTHING ON THIS SHEET WILL BE GRADED